CN109312464A

CN109312464A - The method for preparing halide perovskite and perovskite associated materials

Info

Publication number: CN109312464A
Application number: CN201780034319.8A
Authority: CN
Inventors: D·卡恩; G·霍兹; Y·拉基塔; N·柯德姆
Original assignee: Yeda Research and Development Co Ltd
Current assignee: Yeda Research and Development Co Ltd
Priority date: 2016-05-08
Filing date: 2017-05-08
Publication date: 2019-02-05
Also published as: WO2017195191A1; US20190185495A1; IL245536A0; EP3455391A1; WO2017195191A8

Abstract

The present invention relates to the methods for preparing halide perovskite or perovskite associated materials on substrate, and are related to the photoelectric device and photovoltaic cell of the perovskite comprising preparing by the method for the invention.The method for being used to prepare perovskite includes that metal element or metal alloy are converted into halide perovskite or perovskite associated materials.

Description

The method for preparing halide perovskite and perovskite associated materials

Technical field

The present invention relates to the methods that halide perovskite or perovskite associated materials are prepared on substrate, and comprising passing through The photoelectric device and photovoltaic cell of the perovskite of the method for the present invention preparation.The method for preparing perovskite includes directly by metal element Or metal alloy is converted into halide perovskite or perovskite associated materials.

Background technique

Halide perovskite semiconductor shows unusual rapid advances, present transfer efficiency in terms of photovoltaic performance More than 20%.Although these materials known a very long time, only in past about 25 years, they are just conscientious Ground is considered as electronic material, especially as luminaire and transistor [1], and before they only occur in the several years into photovoltaic research (2012) [2-5].

The material of most study is MAPbI₃, because the band gap (about 1.6eV) of this material is close to the best unijunction sun Band gap needed for energy (photovoltaic) battery.(MA refers to methyl ammonium, CH₃NH₃ ⁺It is abbreviated as MA⁺).The MAPbBr of more high band gap₃(about 2.3eV) For the photovoltaic cell (such as series-connected cell) of spectrum division or pass through photoelectrochemical process productionization as high band gap semiconductor Product also result in many concerns.

The high photovoltaic and photoelectric properties of these materials (are filled derived from the big diffusion length of such as light induced electron and hole due to long The combination of electric life and good charge mobility), the combination of the characteristic of high optical absorption coefficient and low trap density etc.

Have several for manufacturing the universal method of these semiconductor layers:

1. from spin coating in the organic solution of semiconductor or precursor；

2. being evaporated in vacuo；Or

3. spraying coating.

The spin coating of organic solution is especially welcome, because it needs relatively simple equipment and low temperature (energy) input (right It is critically important in following manufacturing process).Solution is one-step method or two-step method.

Prepare MAPbI₃One-step method include for example: will in polar solvent contain MAI and PbI₂Solution be spin-coated on it is required On substrate [6].

Prepare MAPbI₃Two-step method include for example: first by PbI₂Solution is spin-coated on substrate.Then by the solution Or it is handled by MAI steam MAI by the PbI₂Layer is converted into MAPbI₃。[4,7]

In two kinds of spin coating methods, end layer is usually heat-treated at 100-130 DEG C.Spin coating method may also include not Same processing, for example, adding non-solvent [8] during spin coating and annealing [9] in the presence of solvent vapo(u)r.

Organic solvent used in these depositions is toxic mostly: dimethylformamide (DMF) is most common one kind； Dimethyl sulfoxide (DMSO) changes very greatly when it includes the Pb salt of dissolution although itself does not have toxicity；Gamma-butyrolacton (GBL).Therefore, toxicity will be fabrication stage important consideration factor, this may dramatically increase manufacturing cost.

Vacuum evaporation may include multiple sources, have high-caliber control to the evaporation rate of every kind of precursor.However, this Method is less popular, is primarily due to it and inputs with higher complexity and high-energy.

Spraying coating generally includes single source, has high-caliber control to spray rate and base material temperature.Usually spray The liquid of painting is Nitrosamines, the case where with perovskite spraying coating, that is, such.In general, this system need and environment high every From.

Bibliography

1.(i)Mitzi,D.B.in Prog.Inorg.Chem.(ed.Karlin,K.D.)1–121(John Wiley& Sons,Inc.,1999)|DOI:10.1002/9780470166499.ch1；(ii)David B.Mitzi,Templating and structural engineering in organic–inorganic Perovskites,J.Chem.Soc., Dalton Trans.,2001,1–12|DOI:10.1039/B007070J

2.Liu,M.,Johnston,M.B.&Snaith,H.J.Efficient planar heterojunction perovskite solar cells by vapour deposition.Nature 501,395–398(2013).

3.Kim,H.-S.,Lee,C.-R.,Im,J.-H.,Lee,K.-B.,Moehl,T.,Marchioro,A.,Moon, S.-J.,Humphry-Baker,R.,Yum,J.-H.,Moser,J.E.,M.&Park,N.-G.Lead Iodide Perovskite Sensitized All-Solid-State Submicron Thin Film Mesoscopic Solar Cell with Efficiency Exceeding 9%.Sci.Rep.2, (2012)

4.Burschka,J.,Pellet,N.,Moon,S.-J.,Humphry-Baker,R.,Gao,P., Nazeeruddin,M.K.&M.Sequential deposition as a route to high- performance perovskite-sensitized solar cells.Nature 499,316–319(2013).

5.Green,M.A.,Emery,K.,Hishikawa,Y.,Warta,W.&Dunlop,E.D.Solar cell efficiency tables(version 47).Prog.Photovolt.Res.Appl.24,3–11(2016).

6.Kojima,A.,Teshima,K.,Shirai,Y.&Miyasaka,T.Organometal Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells.J.Am.Chem.Soc.131,6050–6051(2009).

7.Chen,Q.,Zhou,H.,Hong,Z.,Luo,S.,Duan,H.-S.,Wang,H.-H.,Liu,Y.,Li,G.& Yang,Y.Planar Heterojunction Perovskite Solar Cells via Vapor-Assisted Solution Process.J.Am.Chem.Soc.136,622–625(2014).

8.Jeon,N.J.,Noh,J.H.,Kim,Y.C.,Yang,W.S.,Ryu,S.&Seok,S.I.Solvent engineering for high-performance inorganic–organic hybrid perovskite solar cells.Nat.Mater.13,897–903(2014).

9.Liu,J.,Gao,C.,He,X.,Ye,Q.,Ouyang,L.,Zhuang,D.,Liao,C.,Mei,J.&Lau, W.Improved Crystallization of Perovskite Films by Optimized Solvent Annealing for High Efficiency Solar Cell.ACS Appl.Mater.Interfaces 7,24008–24015(2015).

Summary of the invention

In one embodiment, the present invention provides a kind of preparation formula A_uB_vX_wHalide perovskite or perovskite it is related The method of material；

Wherein:

A is at least one monovalence or divalent organic cation, inorganic cation or combinations thereof；

X is at least one halide anions, pseudohalide anion or combinations thereof；

U is between 1-10；

V is between 1-10；

W is between 3-30；

B is at least one metal cation, wherein forming perovskite or the relevant material of perovskite when in conjunction with A and X Material；

Wherein inorganic cation A is different from metal cation B；

The method comprise the steps that

B metal or metal alloy layer is deposited on substrate；With

The B metal or metal alloy layer described in the solution comprising A and X or steam treated, wherein the solution or steam with The B metal or metal alloy reaction, to form formula A in the surface of solids_uB_vX_wHalide perovskite or perovskite it is related Material；

Or

The salt deposit containing A and X is deposited on substrate；With

Salt deposit described in steam treated with B metal or metal alloy；Wherein the B metal or metal alloy and the salt are anti- It answers, to form formula A on the surface of solids_uB_vX_wHalide perovskite or perovskite associated materials.

In one embodiment, the present invention provides halide perovskite prepared according to the methods of the invention or perovskites Associated materials.

In one embodiment, the present invention provides a kind of photoelectric device, and it includes formula A_uB_vX_wHalide perovskite or Perovskite associated materials；

Wherein:

X is at least one halide anions, pseudohalide anion or combinations thereof；

U is between 1-10；

V is between 1-10；

W is between 3-30；

B is at least one metal cation, wherein forming halide perovskite when in conjunction with A and X or perovskite being related Material；

Wherein inorganic cation A is different from metal cation B；

The wherein formula A_uB_vX_wHalide perovskite or relevant perovskite material be to prepare according to the method for the present invention 's.

In one embodiment, the present invention provides a kind of photovoltaic cell, and it includes formula A_uB_vX_wHalide perovskite or Perovskite associated materials；

Wherein:

X is at least one halide anions, pseudohalide anion or combinations thereof；

U is between 1-10；

V is between 1-10；

W is between 3-30；

Wherein inorganic cation A is different from metal cation B；

The wherein formula A_uB_vX_wHalide perovskite or perovskite associated materials be to prepare according to the method for the present invention 's.

Detailed description of the invention

It particularly points out and is distinctly claimed in the conclusion part of specification and be considered as subject of the present invention.However, When read in conjunction with the accompanying drawings, by reference to described in detail below, can be best understood organizing and operating method of the invention with And its objects, features and advantages, in which:

Figure 1A -1D indicates the Pb evaporated on glass slide.The cross of the SEM image of the about 50nm of the Pb evaporated on glass slide Section view (Figure 1A) and plan view (Figure 1B).The about 50nm X-ray diffraction (Fig. 1 C) of Pb evaporating film on glass slide.Glass The image (Fig. 1 D) of the Pb evaporated on glass glass slide.

The reaction process of Fig. 2A -2E expression Pb film and MABr, MAI or FAI.Fig. 2A: at room temperature, d-TiO₂/ FTO/ glass Pb film (about 120nm) on glass substrate reacts in IPA solution with MAI (50mM), MABr (70mM).Fig. 2 B: at room temperature, Pb Film (about 50nm) reacts in IPI solution with FAI (100mM).Fig. 2 C: the glass protected at room temperature is (on a left side for each block diagram Side) with Pb glass slide (right side) and 100mM MABr solution react at room temperature 1 hour (left frame figure) afterwards, after 1 day (Block Diagrams) After 3 days (right block diagram).Fig. 2 D: in d-TiO₂120nm Pb film on/FTO/ glass at -70 DEG C 50mM MABr in IPA Reaction 8 hours.Fig. 2 E:(i) before and after handling (50mM, about 2 hours) with the MAI being dissolved in IPA, in d-TiO₂/ The Pb film (about 100nm) evaporated on FTO/ glass substrate glass.(ii) in 50mM MAI, 70mM MABr and 70mM FABr solution (from left to right) 2 hours are handled at 20 DEG C respectively in, and 4 hours are handled at 50 DEG C, handle similar Pb film within 5 hours in 50 DEG C of processing Perovskite film afterwards.MAPbBr₃And FAPbBr₃The verifying of structural identity can find in figures 3 a and 3b.(iii) and IPA In 50mM MAI solution (on) reaction 1 hour (in) 5 hours and (under) (deposition is on the glass substrate for 28 hours Pb films；About XRD diagram case 150nm).(iv) Pb film of the immersion deposition on glass before 2 hours in the 50mM MAI being dissolved in IPA The plane SEM image (because Pb film does not have dense accumulation, significant reaction is faster) on (left side) and later (right side).

Fig. 3 A shows MAPbI₃And MAPbBr₃The XRD diagram of film, at room temperature Pb film (50nm, on glass) in IPA In 100mM MABr solution reaction 24 hours and with reacted 110 minutes in the 50mM MAI in IPA.In the latter, in XRD Some elements Pbs can be seen in the figure, show that reaction is incomplete.Fig. 3 B shows FAPbBr₃XRD spectrum, by will be deposited on FTO/d-TiO₂The Pb of about 100nm on substrate is immersed in the IPA solution of FABr 80mM 2 hours, and (first hour is in 1V Electrical bias under with Pt reference electrode) obtain (more details are shown in embodiment 12).

Fig. 4 A-4E is presented in 25mM MAI (Fig. 4 A), 50mM MAI (Fig. 4 B), 100mM MAI (Fig. 4 C), 250mM MAI (Fig. 4 D), 500mM MAI (Fig. 4 E) IPA in react the SEM image of the Pb film (about 50nm) reacted on 4 hours glass.

Fig. 5 shows the SEM image of the 120nm Pb film handled with MABr solution: 70mM is heated to about 70 DEG C in IPA； Cross section (left side)；Plan view (right side).

Fig. 6 A shows that the 120nm Pb film being deposited on glass is reacted with the 46mM MAI in IPA at room temperature, containing not With the I of molar percentage₂(relative to MAI).The I of Fig. 6 B-6C:Pb film (about 100nm) and 50mM MAI salt and 10 moles of %₂ (relative to MAI) (Fig. 6 B) and be free of I₂(Fig. 6 C) reacts at room temperature 1 hour plane SEM image.Pb is deposited on FTO.

Fig. 7 A indicates that the 120nm Pb film being deposited on glass is reacted with the 46mM MABr in IPA at room temperature, wherein containing There is the Br of different molar percentages₂(relative to MABr).Fig. 7 B:Pb film (about 100nm) and 50mM MABr salt and 10 moles of %Br₂ (relative to MABr) and be free of Br₂(Fig. 7 C) reacts at room temperature 6 hours plane SEM images.Pb is deposited on glass.

Fig. 8 A shows that Pb film (about 100nm) at room temperature and 50mM MAI salt and 10%HI or TFA sour (relative to MAI) are anti- Answer 1 hour plane SEM image.Pb is deposited on FTO.Fig. 8 B shows Pb film (about 100nm) and 50mM MAI salt and 10%KOH Alkali (relative to MAI) reacts at room temperature 1 hour plan view SEM image.Pb is deposited on FTO.

Fig. 9 is indicated on the glass reacted in the MeOH solution of 80mM CsBr and the solution containing about 50mM HBr about The X-ray diffraction of 100nm Pb film.

Figure 10 A is shown to rub in MABr (in EtOH or IPA), MAI (in IPA) and the MABr:MAI [1:1] of 50mM You are than the optical transmission spectra (correction reflection) of Pb (about 100nm) film reacted in (in IPA).Based on empirical equation E_g= 1.57+0.39x+0.33x², mix Br:I ratio of the band gap corresponding to about 25:75 of perovskite.Spectrum shows MAPbI₃Coverage rate Almost, because at super band gap wavelength %T_corrAlmost zero.The coverage rate of other films is poor, because light passes through Unlapped region transmission (when comparing the reaction in IPA or EtOH, also shows MAPbBr₃(Figure 10 C).According to these light Spectrum calculates MAPbI₃、MAPb(I,Br)₃And MAPbBr₃Optical band gap be respectively 1.55,1.68 and 2.26eV.Figure 10 B is shown in With the SEM image (left side) of the Pb film (about 100nm, on FTO) of 50mM MAI processing about 2.5 hours and in EtOH in IPA The optical microscope image (right side) of reaction film.Figure 10 C show in the 80mM MABr in IPA (left side) or EtOH (right side) with Pb The SEM image of similar reaction in 4 hours occurs for film.

Figure 11 A-11B shows the MAPbI prepared as described in example 10 above₃The transversal cross-section backscatter SEM image of battery The I-V curve (Figure 11 B) of lower battery is shined upon as (Figure 11 A) and in dark and I.

MAPbI is presented in Figure 12 A-12B₃The cross-section SEM images (Figure 12 A) of battery (do not have hole to lead with embodiment 10 The SEM image of body is suitable) and in the dark IV curve (Figure 12 B) for shining upon lower battery with I.

Figure 13 show and handled in the EtOH of the HI containing 0.5M on glass with 0.5M MAI (on) Sn of thermal evaporation The picture of film (about 100nm), and (under) at (the about 0.1M) of saturation to be dissolved in the CsI in the MeOH containing 0.5M HI molten for Sn foil Liquid.

Figure 14 shows the XRD diagram case of black coating after the processing Sn foil of the solution described in Figure 13.Based on data in literature, XRD diagram case is related to planar index.For MASnI₃, diffraction pattern includes major part MAI (being indicated with star), some Sn substrates (using circles mark) and MASnI₃Perovskite (is indicated) with crystal face.For Cs₂SnI₆, it is full that Sn foil immerses the CsI containing 0.5M HI After methanol solution, which is obviously attributed to Cs₂SnI₆(all peaks are and Cs₂SnI₆It is related；Indicated by its crystal face). MASnI₃And Cs₂SnI₆Document mode be based on C.C.Stoumpos etc., Inorg.Chem.52,9019 (2013)

Figure 15 A shows reflection Vis-IR spectrum of the Sn foil of reaction in iodized salt solution (as shown in figure 14).Figure 15 B is aobvious The Tauc figure based on reflectance spectrum is shown, to determine the optical band gap of black coating.About MASnI in the result and document₃ (1.20eV)、FASnI₃(1.41eV) and Cs₂SnI₆The value of the optical band gap of (1.26eV) unanimously [is based on very much C.C.Stoumpos etc., Inorg.Chem.52,9019 (2013) and B.Lee etc., J.Am.Chem.Soc.136,15379, (2014)]。

Figure 16 A-16B is presented in IPA in 50mM MAI or 200mM MABr solution Pb (the about 100nm on FTO) extremely MAPbI₃(Figure 16 A) and MAPbBr₃The electrochemistry assist conversion of (Figure 16 B).Figure 16 A (i) is shown in reference (R) and work (W) electricity Apply about 1 minute reaction system photo after 0.75V between pole.It is all Pt coil to electrode (C) and (R) electrode.Working electrode It is the Pb on FTO/ glass.Brown cloud beside Pb electrode is more iodide that electrochemistry generates.Figure 16 A (ii) is shown 1 hour Afterwards the reaction film of electrochemistry auxiliary plan view (on) and cross section (under) SEM image of view.Figure 16 A (iii) is shown The XRD diffraction pattern of electrochemistry auxiliary and the film of non-electrochemical reaction in 50mM MAI/IPA.Pb- { 111 } peak of disappearance shows to add The reaction rate of speed.Figure 16 B (i) shows apply 1.20V between reference (' R') and work (' W') electrode after about 1 minute Reaction system photo.Counter (' C') and (R) electrode are all Pt coils.W is the Pb evaporating film on FTO glass.Beside Pb electrode Yellow cloud be element B r₂, it is yellow in IPA.The reactive film that electrochemistry assists after Figure 16 B (ii) is shown 1 hour Plan view (on) and cross section (under) SEM image.Figure 16 B (iii) show under similar reaction condition but with and without Apply the XRD diffraction pattern of the reactive film of 1.20V anodic bias to W..{ 111 } peak Pb- disappears after applying the bias 1 hour, Show that reaction rate is accelerated.

Figure 17 shows that (i) prepares the SEM image of the cross section of the battery of halide perovskite in electrochemistry householder method (in both cases in the 50mM MAI (left side) in IPA and 80mM MABr (right side) solution for Pt electrode apply 1V (and Ag/AgI FTO/d-TiO) is arrived₂Continue 20 minutes on/Pb substrate.(ii) such as the MAPbI of formation perovskite in (i)₃And MAPbBr₃ The dark and light (solar simulation 100mW/cm of battery²) I-V sweep.

Figure 18 shows the control of the Pb transformation (can accelerate, slow down or invert) to the function as the electrical bias applied The demonstration of system.The sample of shooting: (i) is deposited on the unreacted Pb film on glass；(ii) by the Pb film being deposited on glass with 50mM MAI (left side) in IPA reacts under -0.58V electrical bias and SHE 5 minutes and (right side) and the electrode disconnection (electricity in solution Position is measured as about -0.25V (iii) MAPbI₃In FTO (being obtained after converting Pb) in the solution similar with (i) but in -1.08V Lower reaction.All current potentials are measured and are then converted into SHE scale with Ag/AgI.

Figure 19 A-19C is shown in IPA with the photic hair of time resolution of the MAI and MABr Pb film (on glass) handled Light spectrum.Figure 19 A:Pb film is reacted with 50mM MAI and 70mM MABr.Figure 19 B:Pb film adds at 70 DEG C with different from MABr Agent is added to react.Figure 19 C: the Pb film reacted at room temperature with different additive with MAI.Reaction time is different with reaction solution and becomes Change.

It should be appreciated that in order to illustrate it is simple and clear, element shown in figure is not drawn necessarily to scale.For example, being For the sake of clear, the size of some elements may be exaggerated relative to other elements.It, can be in addition, in the case where being deemed appropriate Repeat reference numerals are in the accompanying drawings to indicate corresponding or similar element.

Specific embodiment

In the following detailed description, numerous specific details are set forth in order to provide thorough understanding of the present invention.However, this Field the skilled person will understand that, the present invention can be practiced without these specific details.In other cases, many institutes Known method, process and component is not described in, in order to avoid the fuzzy present invention.

In one embodiment, the present invention relates to the methods for preparing halide perovskite or perovskite associated materials.This The major advantage of invention is reduction of the toxicity of solution used in this method.In addition, metal (mainly Pb) is in manufacture view It is more much lower than the salt toxicity of same metal.Further advantage is that preparing for perovskite prepared by the method for the present invention is simple Property and good form control.The present invention is provided metal element or alloy to halide perovskite or perovskite associated materials Directly convert.

Wherein:

X is at least one halide anions, pseudohalide anion or combinations thereof；

U is between 1-10；

V is between 1-10；

W is between 3-30；

Wherein inorganic cation A is different from metal cation B；

The method comprise the steps that

B metal or metal alloy layer is deposited on substrate；With

The B metal or metal alloy layer described in the solution comprising A and X or steam treated, wherein the solution or steam with The B metal or metal alloy reaction, with the formula A formed in the surface of solids_uB_vX_wHalide perovskite or Perovskite Phase Close material；

Or

The salt deposit containing A and X is deposited on substrate；With

In another embodiment, halide perovskite is formula ABX₃, in which:

A is any monovalence organic cation, inorganic cation or combinations thereof.

B is at least one metal cation, wherein forming halide perovskite material when in conjunction with A and X；

X is at least one halide anions, pseudohalide anion or combinations thereof.

Halide perovskite (not being that perovskite is relevant) refers to the material with three-dimensional crystalline structure relevant to CaTiO 3 Material.Cube ABX₃Perovskite structure is shared three-dimensional (3-D) network of the octahedral extension of BX6 by angle and is formed, and wherein B is usually divalent Metal, X are halide.12 reconfiguration position holes in biggish A cation filling octahedron.For 3-D perovskite, organic A sun The size in the hole 3-D that the size of ion must be appropriate for by it is limited.For the perovskite structure of perfection filling, A, M and X ion It is (R that the geometry of close contact, which applies condition,_A+R_X2 (R of)=t √_M+R_X), wherein R_A、R_MAnd R_XIt is the ion half of corresponding ion Diameter and the tolerance factor (tolerance factor) must satisfy t ≈ 1.Rule of thumb, for most of cubes or quasi- cube calcium Titanium ore, 1 > t > 0.8.T is remoter from 1, from perfect cube CaTiO₃Structure is also more distorted.

Low-dimensional perovskite (being defined herein as " perovskite is relevant ") is defined as conceptually being derived from 3-D calcium The specific notch of perovskite like structure or the structure of slice.[Mitzi,D.B.,Synthesis,Structure,and Properties of Organic-Inorganic Perovskites and Related Materials,Progress in Inorganic Chemistry,1999,1–121].Their general formula is:

Zero for the orientation race (oriented family) along the cutting of<100>direction:

A’₂A_n-1B_nX_3n+1Or A ' A_n-1B_nX_3n+1；N is between 1-9；

Zero for the orientation race along the cutting of<110>direction:

A’₂A_mB_mX_3m+2Or A ' A_mB_mX_3m+2；M is between 1-9；

Zero for the orientation race along the cutting of<111>direction:

A’₂A_q-1B_qX_3q+3Or A ' A_q-1B_qX_3q+3；Q is between 1-9；

Wherein:

A is monovalence organic cation or inorganic cation；

A ' is any monovalence or divalent organic cation；

Wherein A and A ' is different；

X is at least one halide anions, pseudohalide anion or combinations thereof；With

B is at least one metal cation, wherein forming halide material relevant to perovskite when in conjunction with A and X Material.

In another embodiment, halide perovskite associated materials refer to the material being expressed from the next:

·A’₂A_n-1B_nX_3n+1Or A ' A_n-1B_nX_3n+1；N is between 1-9；

·A’₂A_mB_mX_3m+2Or A ' A_mB_mX_3m+2；M is between 1-9；Or

·A’₂A_q-1B_qX_3q+3Or A ' A_q-1B_qX_3q+3；Q is between 1-9；

Wherein:

A is monovalence organic or inorganic cation；

A ' is any monovalence or divalent organic cation；Wherein A and A ' is different.

In one embodiment, the present invention relates to the methods for preparing halide perovskite or perovskite associated materials.? In another embodiment, the A of halide perovskite or perovskite associated materials prepared according to the methods of the invention is at least A kind of monovalence or divalent organic cation, inorganic cation or combinations thereof.In another embodiment, A is the organic sun of monovalence Ion.In another embodiment, A is monovalent inorganic cations.In another embodiment, A be divalent inorganic sun from Son.In another embodiment, A is divalent organic cation.In another embodiment, A is big monovalence or divalent Organic or inorganic cation.In another embodiment, A is comprising Cs⁺Monovalent inorganic cations.In another embodiment party In case, " organic cation " refers to N (R)₄ ⁺, wherein R is identical or different hydrogen, unsubstituted or substituted C₁-C₂₀Alkyl or not The aryl for replacing or replacing；" organic cation " refers to C (R¹)₃ ⁺；Wherein R¹It is identical or different hydrogen, unsubstituted or substituted C₁-C₂₀Alkyl, unsubstituted or substituted aryl or primary, secondary or tertiary amine.In another embodiment, A includes amido or ammonium, Wherein amido or ammonium are primary, secondary, tertiary or quaternary bases.In another embodiment, A is CH₃NH₃ ⁺、CH(NH₂)₂ ⁺, alkylammonium, Acid amidine, ammonium (NH₄ ⁺)、EtNH₃ ⁺、PrNH₃ ⁺、BuNH₃ ⁺、t-BuNH₃ ⁺, carbonamidine (FA⁺), iodine carbonamidine, bromine carbonamidine, Cs⁺、Rb⁺、Cu⁺。

In another embodiment, A includes more than one monovalence or bivalent cation.Mixed-cation halide calcium Titanium ore or perovskite associated materials include two kinds, three kinds or four kinds different A cations.Halide perovskite or perovskite are related The variation of organic cation has an impact to the structure and/or physical property of perovskite in material.By controlling organic sun used Ion can control the electronic property and optical property of material.For example, the electric conductivity of material can by changing organic cation To increase or decrease.In addition, changing organic cation can be changed the band structure of material, to for example allow to control semiconductor material The band gap of material.

In one embodiment, the present invention relates to preparation formula A '₂A_n-1B_nX_3n+1Or A ' A_n-1B_nX_3n+1；A'₂A_mB_mX_3m+2Or A’A_mB_mX_3m+2；Or A '₂A_q-1B_qX_3q+3Or A ' A_q-1B_qX_3q+3Halide perovskite associated materials method.In another implementation In scheme, A ' is at least one monovalence or divalent organic cation, inorganic cation or combinations thereof.In another embodiment In, A ' is monovalence organic cation.In another embodiment, A ' is monovalent inorganic cations.In another embodiment In, A ' is divalent inorganic cations.In another embodiment, A ' is divalent organic cation.In another embodiment In, A ' is big monovalence or divalent organic or inorganic cation.In another embodiment, A ' is comprising Cs⁺Monovalent nothing Machine cation.In another embodiment, A ' includes amido or ammonium, and wherein amine or ammonium are primary, secondary or tertiary groups.Another In a embodiment, A ' is monovalent organic cation, including CH₃NH₃ ⁺,CH(NH₂)₂ ⁺.In another embodiment, " organic Cation " refers to N (R)₄ ⁺, wherein R is identical or different hydrogen, unsubstituted or substituted C₁-C₂₀Alkyl is unsubstituted or take The aryl in generation；" organic cation " refers to C (R¹)₃ ⁺；Wherein R¹It is identical or different hydrogen, unsubstituted or substituted C₁-C₂₀Alkane Base, unsubstituted or substituted aryl or primary, secondary or tertiary amine.In another embodiment, A ' include more than one monovalence or Bivalent cation.In another embodiment, A ' includes amido or ammonium, and wherein amine or ammonium are primary, secondary, tertiary or quaternary groups. In another embodiment, A ' is CH₃NH₃ ⁺、CH(NH₂)₂ ⁺, ammonium (NH₄ ⁺)、EtNH₃ ⁺、PrNH₃ ⁺、BuNH₃ ⁺、t-BuNH₃ ⁺、 Acid amidine, alkylammonium, carbonamidine [FA⁺(CH(NH₂)₂ ⁺)], iodine carbonamidine, bromine carbonamidine, Cs⁺、Rb⁺、Cu⁺。

As used herein, alkyl can be substituted or unsubstituted linear chain or branched chain saturated group.In another embodiment party In case, alkyl chain has 1-20 carbon atom.In another embodiment, alkyl chain has 1 to 10 carbon atom.Another In a embodiment, alkyl chain has 1 to 5 carbon atom.In another embodiment, alkyl chain has 2 to 10 carbon originals Son.The non-limiting example of alkyl includes: methyl, ethyl, propyl, butyl, amyl, hexyl, heptyl, octyl, nonyl or decyl.

In another embodiment, the substituent group of alkyl includes one or more from the following substituent group: replace or Unsubstituted C₁-C₂₀Alkyl, substituted or unsubstituted aryl (as defined herein), cyano, amido, nitro, alkyl amino, virtue Base amino, acylamino- (arylamino), acylamino- (amido), hydroxyl, oxo, halogenated, thio, carboxyl, ester, acyl group, acyl-oxygen Base, C₁-C₂₀Alkoxy, aryloxy group or halogenated alkyl.In another embodiment, substituted alkyl includes 1-3 substituent group.

Aryl is substituted or unsubstituted aromatic group, in loop section contain 6 to 14 carbon atoms, preferably 6 to 10 A carbon atom.Example includes phenyl, naphthalene, indenyl and indanyl.

Aryl also refers to substituted or unsubstituted heteroaryl, monocycle or bicyclic aromatic group, and 6-10 is contained in loop section A atom, including one or more hetero atoms for being selected from O, S, N, P, Se and Si.It can contain such as 1,2 or 3 hetero atom.It is miscellaneous The example of aryl includes thienyl (thiophenyl), pyridyl group, pyrazinyl, pyrimidine radicals, pyridazinyl, furyl, thienyl (thienyl), pyrazolidinyl, pyrrole radicals, oxazolyl, oxadiazoles base, isoxazolyl, thiadiazolyl group, thiazolyl, isothiazolyl, Imidazole radicals, pyrazolyl, quinolyl and isoquinolyl.

In another embodiment, the substituent group of aryl includes one or more selected from substituted or unsubstituted C₁-C₂₀ Alkyl, substituted or unsubstituted aryl (as defined herein), cyano, amino, nitro, alkyl amino, arylamino, acylamino- (arylamino), acylamino- (amido), hydroxyl, oxo, halogenated, thio, carboxyl, ester, acyl group, acyloxy, C₁-C₂₀Alcoxyl Base, aryloxy group or halogenated alkyl.In another embodiment, substituted aryl includes 1-5 substituent group.

In one embodiment, the present invention relates to the methods for preparing halide perovskite or perovskite associated materials.? In another embodiment, the B of halide perovskite prepared according to the methods of the invention or perovskite associated materials is at least one Kind metal cation, wherein forming halide perovskite or perovskite associated materials when in conjunction with A and X.In another implementation In scheme, B is the metal cation that oxidation state is (2+).In another embodiment, B be (II) race metal (Be, Mg, Ca, Sr, Ba) or Group IV metal ((Ga, Sn, Pb), Eu, Zn Cd, Ni, Fe, Co, Cr, Pd, Pt) metal cation.Another In one embodiment, B is the mixture of metal cation, including metal that one or more oxidation state are (+2) and it is a kind of or A variety of oxidation state are the mixture of the metal of (+3) or (+1).The non-limiting example of B alloy includes one or more (II) Race's metal [Be, Mg, Ca, Sr, Ba] or (IV) race metal [(Ga, Sn, Pb), Eu, Zn, Cd, Ni, Fe, Co, Cr, Pd, Pt] with One or more (III) race metal [Bi, Tl, Sb, Ac, In, Ga, Al, P, Rh, Ru, Y, Sc, lanthanide series (Ce, La, Pr, Nd, Sm, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu), Ac, Au, Mn, Ag, Hg] or (I) race metal [Li, Na, K, Rb, Cs] Mixture.

In another embodiment, B Ca²⁺、Sr²⁺、Cd²⁺、Cu²⁺、Ni²⁺、Fe²⁺、Co²⁺、Pd²⁺、Ge²⁺、Bi²⁺、Sn² ⁺、Pb²⁺、As²⁺、In²⁺、Ba²⁺、Mn²⁺、Yb²⁺、Eu²⁺Or combinations thereof.In another embodiment, B is Pb²⁺.In another reality It applies in scheme, B is Sn²⁺.In another embodiment, B is Ge²⁺.In another embodiment, B is Bi²⁺.At another In embodiment, B As²⁺.In another embodiment, B is In²⁺.In another embodiment, B is Ba²⁺.Another In a embodiment, B is Mn²⁺.In another embodiment, B is Sb²⁺.In another embodiment, B is Ca²⁺.Another In one embodiment, B is Sr²⁺.In another embodiment, B is Cd²⁺.In another embodiment, B is Cu²⁺.? In another embodiment, B is Ni²⁺.In another embodiment, B is Fe²⁺.In another embodiment, B is Co²⁺。 In another embodiment, B is Pd²⁺.In another embodiment, B is Yb²⁺.In another embodiment, B is Eu² ⁺.In another embodiment, B includes more than one cation.Mixed-cation perovskite includes two kinds, three kinds or four kinds The cation of different B.

In another embodiment, B as described above is the combination of metal cation or metal cation.At another In embodiment, the method for the present invention includes " deposition B metal or metal alloy layer " or " at B metal or metal alloy steam The step of reason ".These steps are related to using the metal alloy of metal B or B as metal element or alloy.For the method for the present invention Metal element or alloy correspond to the metal cation B that obtains in halide perovskite or perovskite associated materials.For example, Deposition or processing step, including Ca (0), Sr (0), Cd (0), Cu (0), Ni (0), Fe are carried out using metal element or alloy B (0), Co (0), Pd (0), Ge (0), Bi (0), Sn (0), Pb (0), AS (0), In (0), Ba (0), Mn (0), Yb (0), Eu (0) or A combination thereof.

In one embodiment, the present invention relates to the methods for preparing halide perovskite or perovskite associated materials.? In another embodiment, the X of halide perovskite prepared according to the methods of the invention or perovskite associated materials is at least one Kind halide anions, pseudohalide anion or combinations thereof.Term " halide anions " refer to the 7th race's element yin from Son, i.e. halide anion.In one embodiment, " halide anion " refer to fluorine anion, cl anion, bromine anions or Iodine anion.Term " pseudohalide anion " as used herein refers to the polyatomic anion of similar halogen.Pseudohalide The non-limiting example of anion includes SeCN^-、NCSe^-、NCTe^-、SCN^-、CN-、NC^-、OCN^-、NCO^-、NCS^-、BH₄ ^-、OSCN^-、 Co(CO)₄ ^-、C(NO₂)₃ ^-、C(CN)₃ ^-) and N₃ ^-.In another embodiment, X is bromine anions.In another embodiment In, X is iodine anion.In another embodiment, X is fluorine anion.In another embodiment, X is cl anion. In another embodiment, X includes more than one anion.Mixed anion perovskite include two kinds, three kinds or four kinds not Same X anion.

In one embodiment, the present invention relates to the methods for preparing halide perovskite or perovskite associated materials.? In another embodiment, the u of halide perovskite or perovskite associated materials prepared according to the methods of the invention is 1 to 10 Integer.In another embodiment, 1 u.In another embodiment, u is 2.In another embodiment, u is 3.In another embodiment, u is between 2-10.In another embodiment, halogenation prepared according to the methods of the invention The v of object perovskite or perovskite associated materials is integer of 1 to 10.In another embodiment, 1 v.In another implementation In scheme, v 2.In another embodiment, 3 v.In another embodiment, v is between 2-10.In another reality It applies in scheme, the integer that the w of halide perovskite prepared according to the methods of the invention or perovskite associated materials is 3 to 30.? In another embodiment, w 3.In another embodiment, 4 w.In another embodiment, 5 w.Another In a embodiment, w 6.In another embodiment, w is between 3-10.

In one embodiment, the present invention relates to the methods for preparing halide perovskite associated materials.In another reality It applies in scheme, the integer that the n in halide perovskite associated materials prepared according to the methods of the invention is 1 to 9.In another reality It applies in scheme, n 1.In another embodiment, 2 n.In another embodiment, 3 n.In another embodiment party In case, n is between 2 to 9.In another embodiment, halide perovskite correlation material prepared according to the methods of the invention The integer that the m of material is 1 to 9.In another embodiment, 1 m.In another embodiment, 2 m.In another reality It applies in scheme, m 3.In another embodiment, m is between 2 to 9.In another embodiment, square according to the present invention The integer that the q of the halide perovskite associated materials of method preparation is 1 to 9.In another embodiment, 1 q.At another In embodiment, q 2.In another embodiment, 3 q.In another embodiment, q is between 2 to 9.

In one embodiment, the present invention relates to the methods for preparing halide perovskite or perovskite associated materials.? In another embodiment, this method includes the deposition B metal or metal alloy layer in substrate.In another embodiment, B Metal or metal alloy (metal element is not the cationic form of B) is deposited on substrate.In another embodiment, lead to Any method known in the art is crossed in deposited on substrates B metal or metal alloy layer.In another embodiment, B metal Or metal alloy passes through hydatogenesis on substrate.In another embodiment, B metal or metal alloy is heavy by electro-deposition Product is on substrate.In another embodiment, B metal or metal alloy is deposited on substrate by electroless plating process.Another In one embodiment, the thickness of B layers of metal or metal alloy is determined by the perovskite of the method for the present invention preparation on substrate Purposes.For example, thickness is approximately the optical absorption depth of perovskite, usually several hundred nanometers for photovoltaic application.For photoelectricity Device, thickness can change between superthin layer (a few nm) and at least several μm.In another embodiment, these are answered With thickness is between 1-1000nm.In another embodiment, with a thickness of 1-100nm.In another embodiment, thick Degree is 1-10nm.In another embodiment, with a thickness of 1-5 μm.In one embodiment, it is if it happens fully converted to Halide perovskite or perovskite associated materials, then the thickness for converting metal B will be by the total thickness of the metal or metal alloy deposited Degree determines.In one embodiment, the Pb of deposition is presented in Figure 1A -1D in glass microscope slide.

In one embodiment, the method for the present invention includes with the solution comprising A and X or steam treated B metal or gold The step of belonging to alloy-layer, wherein the solution or steam react to be formed in the surface of solids with the B metal or metal alloy Formula A_uB_vX_wHalide perovskite or perovskite associated materials.In another embodiment, solution or steam comprising A and X Include: ammonium and halide, wrap amine-containing organic cation and halide, carbonamidine and halide, ammonium and pseudohalide, carbonamidine and intend Halide wraps amine-containing organic cation and pseudohalide, monovalent metal cation and halide, monovalent metal cation and intends Halide, divalent metal and halide, divalent metal and pseudohalide or combinations thereof.Non-limiting example packet It includes: CH₃NH₃I (=methylpyridinium iodide ammonium, MAI), CH₃NH₃Br (=methyl bromide ammonium, MABr), CH (NH₂)₂I (carbonamidine iodide, FAI), CH (NH₂)₂Br (carbonamidine bromide, FABr), C (I) (NH₂)₂I (iodomethyl iodine amidine iodide), CsI, CsBr, RbI and RbBr。

It is the solubility of the wherein material comprising A, A' and X much higher than product (halogen for the solvent of solution, including A and X Compound perovskite or perovskite associated materials) solubility or B metal or metal alloy solubility any solvent.Another In a embodiment, solvent is polar solvent.In another embodiment, solvent be alcohol, acetonitrile, the solvent with nitro, Solvent with carboxyl, the solvent with cyano.In another embodiment, solvent be methanol, acetonitrile, isopropanol, ethyl alcohol, Butanol or combinations thereof.In another embodiment, as the chain length of alcohol increases, reaction rate is reduced.

In another embodiment, the concentration of A and X is 0.1mM to 3M in solution.

In one embodiment, the processing of the film layer of B metal or metal alloy and the solution comprising A and X or steam Step includes that optionally addition includes halogen (F₂、Cl₂、Br₂、I₂)、HI、HCl、HBr、HF、HCN、S(CN)₂, alkyl halide, halogenated virtue The external additive of hydrocarbon, haloheteroaromatic, halogenated cycloalkane, reducing agent, haloid or combinations thereof.In one embodiment, Alkyl halide refers to alkyl as defined above, is replaced by one or more halogen atoms, for example, by F, Cl, Br or I, it is halogenated The non-limiting example of alkyl is CF₃、CF₂CF₃、CH₂CF₃。

In one embodiment, halogenated aryl hydrocarbon refers to aromatic hydrocarbons as defined above, is taken by one or more halogen atoms Generation, such as by F, Cl, Br or I, the non-limiting example of halogenated aryl hydrocarbon group be bromophenyl, chlorphenyl, Isosorbide-5-Nitrae-dichlorophenyl, Iodophenyl, Isosorbide-5-Nitrae-diiodo- phenyl.

In one embodiment, haloheteroaromatic refers to the heteroaryl replaced by one or more halogen atoms, such as Pass through F, Cl, Br or I.Heteroaryl refers to aryl as defined above, wherein one or more carbon atoms are by sulphur, oxygen, nitrogen or its What combination replaces.The non-limiting example of haloheteroaromatic is chloropyridine, iodine pyridine, bromopyridine, bromo indole, iodine indoles, fluorine quinoline Quinoline, iodine quinoline, bromoquinoline.

In one embodiment, halogenated cycloalkane refers to the Heterocyclylalkyl replaced by one or more halogen atoms, example Such as, Heterocyclylalkyl refers to that saturation ring structure, carbon atom also include a part of sulphur, oxygen, nitrogen or any combination thereof as ring. In another embodiment, Heterocyclylalkyl is 3-12 member ring.In another embodiment, Heterocyclylalkyl is 6 member rings.It is halogenated The non-limiting example of cycloalkane is Chloperastine, iodine piperidines, bromine piperidines, bromine pyrroles, iodine morpholine, flumorph, bromine morpholine.

In one embodiment, reducing agent refers to the reagent that stabilized metal can be made in required oxidation state, for example, anti- The Sn of block²⁺It is further oxidized to Sn⁴⁺.The non-limiting example of reducing agent is NaBH₄Or H₃PO₂。

In one embodiment, haloid includes the haloid of B metal or metal alloy, wherein SnF₂Or PbF₂It is this The example of class.

In another embodiment, the concentration of external additive is 0.05% to 25% (mole % in solution；Relative to Salt).

In one embodiment, the method for the present invention includes with the metal of the solution containing A and X or steam treated B or The step of alloy-layer.In another embodiment, processing step carries out at room temperature.In another embodiment, it handles Step 10-150 DEG C at a temperature of carry out.In another embodiment, temperature is 15-80 DEG C.In another embodiment In, temperature is 20-100 DEG C.

Embodiment 1-8 provides the embodiment of the method for the present invention.

In one embodiment, the method that the present invention prepares halide perovskite or related perovskite includes with containing A The step of with the metal or alloy layer of the solution of X or steam treated B.In another embodiment, preparation method can pass through Apply electrical bias on the different layers to control halide perovskite or relevant perovskite；For example, by metal or metal conjunction The anodic oxidation of metal and/or X in gold surface^-Oxidation, the reaction can be accelerated.In another embodiment, molten in alcohol Positive bias is applied to the B metal or metal alloy layer of deposition in liquid.In another embodiment, electrochemistry (anode) reaction exists It carries out under positive bias, preferably for MAX, is carried out between+0.25V and+1.0V.Electrolysis can also under the conditions of non-DC (such as Pulse current) it carries out, and be very different in this situation current potential.In another embodiment, this method is reversible.

In another embodiment, electrochemical reaction is described in embodiment 12 and Figure 16 A-16B.

In one embodiment, the present invention relates to the methods for preparing halide perovskite or perovskite associated materials.? In another embodiment, this method includes the salt deposit that deposition includes A and X in substrate.

In another embodiment, salt deposit is deposited on substrate by any method known in the art.? In another embodiment, by evaporation or solution methods (spin coating, spraying, silk-screen printing) by mineralization on substrate.

In another embodiment, the thickness of salt deposit is determined by the perovskite of the method for the present invention preparation on substrate Purposes.For example, thickness is approximately the optical absorption depth of halide perovskite or perovskite associated materials for photovoltaic application, lead to It is often several hundred nanometers.For photoelectric device, thickness can change between superthin layer (a few nm) and at least several μm.These are answered With in another embodiment, thickness is between 1-1000nm.In another embodiment, with a thickness of 1-100nm.? In another embodiment, with a thickness of 1-10nm.In another embodiment, with a thickness of 1-5 μm.In an embodiment In, halide perovskite or perovskite associated materials are if it happens fully converted to, then the thickness of salt deposit is by the metal by depositing Or the overall thickness of metal alloy determines.

In another embodiment, the salt comprising A and X includes: alkyl ammonium halide, ammonium halide organic cation, packet Include amine and halide；Carbonamidine halide；Alkylammonium pseudohalide, ammonium halide, formyl amidine pseudohalide, monovalent metal cation- Halide, monovalent metal cation-pseudohalide；Divalent metal-halide, divalent metal-pseudohalide, Alkylamide-halide, acid amidine-pseudohalide or combinations thereof.Non-limiting example includes: CH₃NH₃I (=methylpyridinium iodide ammonium, MAI), CH₃NH₃Br (=methyl bromide ammonium, MABr), CH (NH₂)₂I (carbonamidine iodide, FAI), CH (NH₂)₂Br (carbonamidine bromination Object, FABr), C (I) (NH₂)₂I (iodine carbonamidine iodide), CsI, CsBr, RbI and RbBr.In one embodiment, of the invention Method include the steps that the steam treated salt deposit with B metal or metal alloy；Wherein the B metal or metal alloy with it is described Reactant salt forms formula A in the surface of solids_uB_vX_wHalide perovskite or perovskite associated materials.

In one embodiment, the method for the present invention includes in deposited on substrates B metal or metal alloy layer or in base The step of deposition includes the salt deposit of A and X on material.In another embodiment, this layer is film, quantum continuously or discontinuously Point, porous layer etc..

In one embodiment, the method for the present invention includes in deposited on substrates B metal or metal alloy layer or in base The step of deposition includes the salt deposit of A and X on material.In another embodiment, substrate is any substrate.In another embodiment party In case, substrate is planar substrate.In another embodiment, substrate is carbon-based GaAs ceramic material, is contained from The ion of III and V race；Ceramic material, glass, electro-conductive glass, coated glass, metallic film containing II-VI group ion or Thin slice, nanometer or mesoporous matrix, mesoporous oxide, d-TiO₂/ FTO (fluorine-doped tin oxide), ITO, (100) p-type (boron-doping) Si, N-shaped (phosphorus doping) Si, the fine and close TiO on the glass of fluorine-doped tin oxide (FTO) coating₂(d-TiO₂) or combinations thereof.Another In a embodiment, substrate is glass.In another embodiment, substrate is electro-conductive glass.In another embodiment, Substrate is glass, is coated by conductive material.In another embodiment, substrate is carbon based substrate.In another embodiment In, substrate is GaAs.In another embodiment, substrate is the ceramic material containing the ion from Section III and V race.? In another embodiment, substrate is the ceramic material containing the ion from II-VI group.In another embodiment, Substrate is metal plate.In another embodiment, substrate is metal film.In another embodiment, substrate be nanometer/in Hole substrate.In another embodiment, matrix is nano particle.In another embodiment, substrate is mesoporous oxide. In another embodiment, substrate is nano-porous materials.In another embodiment, substrate is the tin oxide of Fluorin doped (FTO) glass coated.In another embodiment, substrate is the glass of tin oxide (FTO) coating of Fluorin doped.Another In a embodiment, substrate is p-type (boron doped) Si.In another embodiment, substrate is undoped p-type-Si.Another In a embodiment, substrate is d-TiO₂The glass of/FTO coating.In another embodiment, substrate is glass, conductive glass Glass, coating glass, metal film or piece, nanometer or mesoporous porous substrate, mesoporous oxide, d-TiO₂/ FTO (fluoro- tin oxide), (100) p-type (boron doping) Si, the fine and close TiO on the glass of fluorine-doped tin oxide (FTO) coating₂(d-TiO₂) or combinations thereof.

As used herein, term " mesoporous " refer to the hole in porous layer be it is microcosmic and have size, effectively with Nanometer (nm) measurement.The average pore size in the hole in " mesoporous " structure can be such as 1nm to 100nm, or such as 2nm to 50nm's Any value.Each hole can be different size, and can be any shape.In one embodiment, semiconductor is more Aperture layer includes TiO₂.More generally, porous layer includes mesoporous oxide.

In another embodiment, substrate is stable to procedure of processing and the good quality of embryo deposit is allowed to deposit Any material.

In one embodiment, using generally acknowledged upward expansible (up-scalable) technology (such as VLSI processing, Shadow mask evaporation of metal, plating or electroless plating process, the substrate of single layer processing etc.) by (the metal/metal alloy of B includes A With the salt of X) embryo deposit patterning is on substrate.

The thickness of obtained halide perovskite or perovskite associated materials is by original metal/alloy or salt deposit Thickness determines.It can be by the composition of embryo deposit object and the composition of processing step come control composition.

When determining device/battery property, the form of halide perovskite or perovskite associated materials is extremely important.Phase The form of prestige depends on the desired use of halide perovskite or perovskite associated materials.Salinity, solution processing temperature with And the property for the solvent and additive being added in salting liquid influences device/battery form and property.

In one embodiment, halide perovskite or perovskite associated materials prepared according to the methods of the invention are MAPbI₃、MAPbBr₃、MAPb(Br,I)₃、FAPbI₃、FAPbBr₃、FAPb(Br,I)₃、CsPbI₃、CsPbBr₃Or CsPb (Br, I)₃、(Cs,FA)PbI₃、MA(Pb,Sn)I₃.

Using

In one embodiment, the present invention provides a kind of photoelectric device, and it includes halogen prepared according to the methods of the invention Compound perovskite or perovskite associated materials.

In one embodiment, the present invention provides a kind of photovoltaic cell, and it includes halogen prepared according to the methods of the invention Compound perovskite or perovskite associated materials.

Halide perovskite and perovskite associated materials prepared according to the methods of the invention is used for manufacture of solar cells.? In one embodiment, unijunction solar cell includes that halide perovskite prepared according to the methods of the invention or perovskite are related Material.In one embodiment, the high photon energy cell for supplementing other currently manufactured (for example, Si) solar batteries includes Halide perovskite or perovskite associated materials prepared according to the methods of the invention.

In one embodiment, the present invention relates to a kind of photoelectric devices, and it includes formula A_uB_vX_wHalide perovskite or Perovskite associated materials；

Wherein:

X is at least one halide anions, pseudohalide anion or combinations thereof；

U is between 1-10；

V is between 1-10；

W is between 3-30；

Wherein inorganic cation A is different from metal cation B；

Wherein:

X is at least one halide anions, pseudohalide anion or combinations thereof；

U is between 1-10；

V is between 1-10；

W is between 3-30；

Wherein inorganic cation A is different from metal cation B；

In one embodiment, photoelectric device of the invention or photovoltaic cell include first electrode, second electrode, set Thin layer between the first electrode and the second electrode is set, which includes perovskite prepared according to the methods of the invention.At one In embodiment, it is anode and cathode that photoelectric device of the invention, which includes first electrode and second electrode, one of them or two A is transparent to allow light to enter.

The selection of the first and second electrode of photoelectric device/photovoltaic cell of the invention may depend on structure type.In general, N-layer is deposited on transparent conductive oxide (TCO), such as tin oxide, is more typically deposited on the tin oxide (FTO) of Fluorin doped It is usually transparent or trnaslucent materials on anode or on tin indium oxide (ITO).Therefore, first electrode be usually it is transparent or It is translucent and generally include FTO or ITO.In general, first electrode with a thickness of 200nm to 1 μm, preferably 200nm is extremely 600nm, more preferably 300 to 500nm.For example, thickness can be 400nm.In general, FTO is coated on glass plate.At one In embodiment, (when electrode is addressed with collection " hole " (i.e. positive charge)), second electrode includes high-work-function metal, such as Gold, silver, nickel, palladium or platinum, and be usually silver.In another embodiment, carbon is (in any form, such as graphite, graphite Alkene, carbon paste or fullerene) it also is used as second electrode.In one embodiment, second electrode with a thickness of 50nm extremely 250nm, preferably 100nm are to 200nm.For example, the thickness of second electrode can be 150nm.

As used herein, term " thickness " refers to the average thickness of the component of photoelectric device.

In one embodiment, photoelectric device of the invention or photovoltaic cell include: first electrode；Second electrode；And And it is arranged between the first and second electrodes: (i) semiconductor layer；(ii) perovskite prepared according to the methods of the invention.

Term " semiconductor " used herein refers to the medium sized material of conductivity between conductors and insulators.Half Conductor can be intrinsic semiconductor, n-type semiconductor or p-type semiconductor.The example of semiconductor includes halide perovskite or calcium titanium Mine associated materials；Titanium, niobium, tin, zinc, cadmium, copper or lead oxide；Antimony, copper, zinc, iron or bismuth chalcogenide (such as copper sulfide And iron sulfide)；Copper-zinc-tin-sulfur category compound, for example, copper zinc tin sulfide, such as Cu₂ZnSnS₄(CZTS) and copper-zinc-tin-sulfur selenides, Such as Cu₂ZnSn(S_1-xSe_x)₄(CZTSSe)；Copper and indium chalcogenide, such as copper indium selenide (CIS)；Copper indium gallium sulphur category compound, such as copper and indium Gallium selenium (CuIni_-xGa_xSe₂)(CIGS)；Or copper indium callium diselenide (CIGS) compound.Further example is Group IV semiconductor and compound Semiconductor (such as silicon, germanium, silicon carbide)；Group iii-v semiconductor (such as GaAs)；II-VI group semiconductor (such as selenizing Cadmium)；I-VII race semiconductor (such as stannous chloride)；Group IV-VI semiconductor (such as lead selenide)；V-VI race semiconductor (such as bismuth telluride)；With Section II-V race semiconductor (such as Cadmium arsenide)；Ternary or quaternary semiconductor (such as Cu-In selenide, copper Indium gallium diselenide, copper zinc tin sulfide or copper zinc tin sulfide selenides (CZTSSe).

In one embodiment, photovoltaic cell includes hole conductor.In another embodiment, hole conductor is Spiral shell-OMeTAD ((two fluorenes of 2,2', 7,7'- tetra--(bis--p-methoxyphenyl of N, N-) 9,9'- spiral shell)), P3HT ((poly- (3- hexyl thiophene Pheno)), PCPDTBT (it is poly- [2,1,3- diazosulfide -4,7- diyl [bis- (2- the ethylhexyl) -4H- cyclopentanos of 4,4- [2,1-b: 3,4-b'] Dithiophene -2,6- diyl]]), PV (poly- (N- vinyl carbazole)), (1- hexyl -3- methylimidazole is double by HTM-TFSI (trifyl) acid imide), Li-TFSI (bis- (trifyl) imide lis) or tBP (tert .-butylpyridine).Another In one embodiment, hole conductor is inorganic hole conductor, such as NiO, CuSCN or Cu₂O。

In another embodiment, photovoltaic cell includes with lower layer: glass/FTO/d-TiO₂/ halide perovskite or Perovskite correlation/spiral shell-OMeTAD/AU.In another embodiment, photovoltaic cell includes with lower layer: glass/FTO/d- TiO₂/ halide perovskite or perovskite correlation/Au.

In one embodiment, photoelectric device is phototransistor.In one embodiment, photoelectric device is two pole of photoelectricity Pipe, including light emitting diode.In one embodiment, photoelectric device is photo resistance.In one embodiment, photoelectric device is Photoelectric detector.

In one embodiment, photoelectric device of the invention is the photic high voltage power supply for decomposing water to generate hydrogen. In one embodiment, photoelectric device of the invention is photic high voltage power supply, is used for CO₂Reduction to produce fuel.At one In embodiment, opto-electronic device of the invention will be mentioned by light for the photic high voltage power supply of chemistry redox reaction For power.

In one embodiment, device/battery of the invention includes more than one halide perovskite or perovskite Relevant layers, wherein every kind of perovskite can be prepared by means of the present invention.In another embodiment, photoelectric device/photovoltaic Battery includes two or three of different perovskite.

Abbreviation:

d-TiO₂: fine and close titanium dioxide

FA: carbonamidine, CH (NH₂)₂

FABr: carbonamidine bromide, CH (NH₂)₂Br

FAI: carbonamidine iodide, CH (NH₂)₂I

FTO: the tin oxide of Fluorin doped

IPA: isopropanol

MA: methyl ammonium, CH₃NH₃ ⁺

MABr: methyl bromide ammonium, CH₃NH₃Br

MAI: methylpyridinium iodide ammonium, CH₃NH₃I

RT: room temperature

SEM: scanning electron microscope

TCO: transparent conductive oxide

There is provided following embodiment is in order to which the preferred embodiments of the invention are more fully described.However, they should not be by It is construed to limit broad range of the invention.

Embodiment

1 metallic lead of embodiment (Pb) is converted into MAPbX₃

The thermal evaporation of Pb carries out in three kinds of different substrates.

Glass microscope slide

Fine and close TiO on the glass of fluorine-doped tin oxide (FTO) coating₂(d-TiO₂)。

(100) p-type (boron doping) Si

In all three cases, the glossiness Pb metal layer with controlled thickness is obtained.Powder x-ray diffraction (XRD) and scanning electron microscope (SEM) image (

Figure 1A -1D) and with the evaporation Pb of about 50 or about 120nm thickness concentration optimization is carried out in the form of optimizing roughly.

The Pb of evaporation is placed on equipped with 0.05-0.1M methylpyridinium iodide ammonium (MAI), methyl bromide ammonium (MABr) and carbonamidine iodine In the bottle of the various alcoholic solutions of compound (FAI).The methanol solution reaction of MAI is very fast, and substantially loses from substrate Carve layer.Ethyl alcohol MAI is converted into black coating for glittering Pb layers of silver gray.Reaction at room temperature is immediately begun to.But turn completely It changes film and needs longer time (several hours).Fig. 2 E (i) shows this conversion (using 50mM MAI).Fig. 2 E (iii) is aobvious The XRD diagram of the film of Partial Conversion is shown, wherein the peak metal Pb is at about 31 degree as the qualitative guidance of transforming degree.

Conversion ratio depends on halogen ion.MABr to MAPbBr₃Reaction ratio MAI to MAPbI₃Reaction it is slow, and need to compare The MABr of iodide higher concentration and/or higher temperature (in Fig. 2 E (ii) -).Keep Pb film and 70mM MABr anti-at 50 DEG C It answers 4 hours, and is fully converted to MAPbBr₃。FAPbBr₃It is also so (Fig. 2 E (ii)-is right).Reaction rate between FA and MA Without very big difference, although MA rate is slightly lower).During FAI reaction, it is easy to identification conversion completely, because orange MA- (or FA)PbBr₃In unreacted Pb show visual gray color, it is opposite (Fig. 2 E (iii)) with complete conversion.About 50nm Pb film layer reacts about 2-3 hours with MAI/IPA and is fully converted to MAPbI₃Black film, and with MABr/IPA (MAPbBr₃Orange Color film) and FAI/IPA (yellow δ-FAPbI₃) needed for about one time be converted into brown film layer.

The property of alcohol influences conversion ratio and film form (Figure 10 B)；The molecular weight of alcohol is lower, converts faster.Compared with IPA, With reacting faster for EtOH, but film quality is worse, is more controlled with reacting for IPA.The case where for MeOH, metal film is completely molten Solution is in the solution.Compared with butanol, react slower with isopropanol (IPA).

When organic cation is changed to inorganic cation i.e. Cs, since dissolubility of the CsX salt in IPA is poor, IPA is no longer The suitable solvent of Pb conversion reaction.Therefore, no matter when using completely inorganic AX salt, MeOH is a kind of more suitably molten Agent, because the solubility in wherein CsBr is quite high (and can increase with the presence (such as HBr) of salt) (Fig. 9).

Influence conversion ratio other factors include:

Pb layers of porosity.Kong Yue is more, and Pb layers of density are lower, reacts faster.Since the volume that Pb is converted into perovskite is swollen Swollen is about 3 times, therefore fine and close calcium titanium ore bed (Fig. 2 E (iv)) is formed by porous Pb layers.

Sour (HI, HBr, TFA (trifluoroacetic acid)) is added and slightly increases rate, but usually increase degree will not be very big.

Based on visual observation, adds free bromine or iodine and slightly increase conversion ratio to a certain extent, be when at least starting In this way.From the acid it is faint yellow in as can be seen that free halogen be usually present in HI solution with the degree of very little (such as in water In), and this color with storage time and can be exposed to air and light and increase.

The various parameters of above-mentioned influence conversion reaction rate also influence perovskite form.It shows by changing solution parameter SEM image plan view (MAI concentration-Fig. 4 A-4E of the film of preparation；Acidity-Fig. 8 A, 8B；Addition element halogen-Fig. 6 A, 6B and 7A,7B)

Converting various perovskites for Pb makes about 3 times of volume expansion: the Pb film of 120nm is changed into the calcium titanium of about 360nm Mine.

By the crystal structure (Fig. 3 A) of XRD analysis reaction film, show that film is MAPbI₃And MAPbBr₃。

In general, as expected, the film formed by faster conversion rate is made of (more smaller crystal The bigger smaller final crystalline size of cuclear density-of the faster nucleation-of fast rate -).This is to increase MAI concentration (Fig. 4 A-4E) The case where with acidity (Fig. 8 A and 8B) is increased, although the rate of higher pH (KOH) solution and MAI solution standard are (in IPA 50mM, no other additives) it is not significantly different.Addition element halogen is to MAPbI₃And MAPbBr₃Form have significantly affect (Fig. 6 A, 6B and 7A, 7B).Obviously, reaction rate is not the single factor for determining crystalline size.It should be noted that biggish Crystalline size does not necessarily mean that better PV battery: biggish crystal generally means that poor substrate covering, this may Lead to the hole in film, leads to the shunting in battery.

Embodiment 2 MAX (X=Br, I) concentration is to MAPbX₃The influence of film layer form

Influence of MAX (X=Br, the I) concentration to film form is as follows.

Fig. 4 A-4E shows MAX:500mM, 200mM, 100mM, 50mM and 20mM of 5 kinds of various concentrations.It is immediately seen increasing Two effects of salt content are that crystalline size reduces and the inhomogeneities of film increases.Another influence is that the cracking of film occurs In higher concentration.For solar battery purposes, the optimum value between big crystal and good covering (small crystals) is generated in 50- Under the concentration of 70mM.

Film form is extremely important in terms of determining film character.Required form depends on the desired use of film or material.

3 temperature of embodiment and solvent are to MAPbX₃The influence of film layer form

The processing of lower temperature provides preferably whole coverage rate (Fig. 7 C), and higher temperature give it is average bigger and More anisotropic crystal (Fig. 5).Replace IPA to handle to obtain bigger crystal with ethyl alcohol, but coverage rate it is worse (Figure 10 A, 10B)。

Influence of the 4 addition element halogen of embodiment to MAPbX3 film shape

Addition element halogen can form polyhalide with MAX salt (X=Br or I), also influence film layer form.Fig. 6 A- 6C shows the effect being added to the elemental iodine of incrementss in the IPA solution of MAI.Although the iodine added at low concentrations is almost It does not influence, but at high concentration (10%), there are strong crystal grain refinements, this typically results in better covering.

Using elemental bromine to MAPbBr₃Same treatment also very strongly influence MAPbBr₃, but mode is not identical.It is brilliant Body, which is grown in the low-down situation of bromine concentration, to be occurred, almost without apparent difference under intermediate concentration, and in high concentration Under, crystal regrows and crystal orientation also changes (Fig. 7 A-7C).To Fig. 7 B-7C examine also show with Bromine concentration increases, and the trend for forming nanometer rods increases.

Embodiment 5 mixes MAPb (I, Br)₃

The method for preparing halide perovskite and perovskite associated materials allows the flexibility of sizable composition.Figure 10 A In show an example of such case.For pure iodide and bromide, the absorption at 810nm and 560nm is risen respectively Begin to absorb corresponding to the expected of these compounds.When the 50:50 mixture of MAI and MABr is for absorbing starting when converting In 755nm.This is equivalent to the I content more much bigger than Br content, this is not surprised, because reacting for MAI and Pb is faster than MABr It is more.

Pb is evaporated on glass, and in IPA with 50:50 (mole) mixture of MAI and MABr be converted into MAPb (I, Br)₃.Figure 10 A shows transmitted spectrum (green figure), shows the optical band gap and pure iodine of the 1.68eV calculated from spectrum Compound (red) and bromide (green) are compared.

6 metallic tin of embodiment (Sn) is converted into MASnI₃

Prepare the ethyl alcohol or IPA solution of 0.5M HI.MAI (0.5M is between 1.0M) is dissolved in HI solution.It will polishing Sn film (0.125mm thick, 99.9% Sn) immersed in above-mentioned solution (HI+MAI) at ambient conditions about 1 hour, in this phase Between on film formed black coating (Figure 13).XRD (Figure 14) shows that black coating is MASnI₃.Reflectance spectrum (Figure 15 A and 15B) The optical band gap of the film is allowed to be estimated as 1.17eV, this is consistent with literature value (1.20eV).

7 metallic tin of embodiment (Sn) is converted into FASnI₃

The program for following embodiment 6 replaces MAI using FAI.From reflectance spectrometry (Figure 15 A and 15B), measure The optical band gap of 1.33eV, it is consistent with literature value (1.41eV).

8 metallic tin of embodiment (Sn) is converted to Cs₂SnI₆

The CsI of 0.64gr is dissolved in the methanol solution of 0.5M HI, causes to react with Sn foil.Figure 13 is shown in and is somebody's turn to do After CsI/HI solution reaction about 30 minutes, Sn foil is converted into Cs₂SnI₆.Converted product is confirmed by the XRD diagram in Figure 14.Reflection Spectrum (Figure 15 A and 15B) allows the estimated value of the optical band gap of 1.27eV, this coincide well with literature value (1.26eV).

The carrier lifetime of 9 perovskite thin film of embodiment

The measurement of semiconductor quality as these films passes through time resolution luminescence generated by light in perovskite thin film (TRPL) charge life (Figure 19 A-19C) is measured.Figure 19 A is shown for MAPbI₃And MAPbBr₃Service life be respectively 263 Hes 213ns.These values are advantageous compared with through several values of the film of conventional spin coating technique preparation and the monocrystalline of report.These Life value depends on MAX solution composition (Figure 19 B-19C), shows that they can be further increased.

10 MAPbI of embodiment₃Photovoltaic cell.

In d-TiO₂120nm Pb is evaporated in/FTO substrate, is handled 6 hours with the IPA solution of 50mM MAI, it is clear in IPA It washes and dries under nitrogen flowing as described in Example 1.Then mixed with 18mM Li-TFSI (bis- (fluoroform) sulfimide lithiums Salt) chlorobenzene in coated by the spiral shell-OMeTAD of spin coating 80mM, obtaining average overburden cover is about 0.75 μm and two Silica-filled seal box stays overnight aging, reacts Li-TFSI with oxygen, to improve the electrical property of hole conductor.Then exist Pass through shadow mask (0.032cm on above-mentioned sample²Area) gold of thermal evaporation 200nm in film layer.Note that with other most of solution Method is compared, and perovskite is not annealed.The X cross-sectional image of device is shown in Figure 12 A-12B and in the dark and in 1 sun I-V curve under irradiation.

In the case where simulating 1 solar radiation, the short current density (J of the device_sc) it is 6.06mA/cm², open-circuit voltage (V_oc) be 0.92V, fill factor (FF) are 44.7%, and whole photoelectric conversion efficiency is 2.5%.

11 MAPbBr of embodiment₃Photovoltaic cell

Manufacture photovoltaic cell as in Example 10, there are two main differences for tool:

1. replacing MAI to form MAPbBr using MABr (70mM)₃。

2. being used without hole conductor (spiral shell-OMeTAD), gold directly evaporates on perovskite.

Figure 11 A shows that the SEM image of the cross section of battery (is led compared with the SEM image in embodiment 10, but without hole Body.In the case where simulating 1 solar radiation, the curve (Figure 11 B) of I-V shows the short current density (J of the device_sc) it is 1.2mA/cm², open Road voltage (V_oc) it is 1.21V, fill factor (FF) is 43.8%, and whole photoelectric conversion efficiency is 0.62%.Note that with front Embodiment is compared, and the optical band gap of perovskite wants much higher in the battery, it means that the current density of battery (and whole effect Rate) it can reduce, but open-circuit voltage can be higher.The battery (such as series-connected cell) or photochemical that this high-tension battery divides spectrum It is especially significant to learn reaction.

Metal Pb is converted halide perovskite by 12 electrochemistry of embodiment auxiliary

The method of the present invention for being used to prepare halide perovskite or perovskite associated materials optionally includes the electricity of B metal layer Chemical assist conversion.Other than accelerating conversion rate, this selection also allows to control conversion process in a higher degree.

The embodiment demonstrates this electrochemistry assist conversion.Pb layer on glass is immersed in the IPA solution of MAI.Make Use potentiostat as power supply, wherein Pb layers are working electrodes, and Pt spiral is used as counterelectrode and quasi- reference electrode, and (reference Pt is molten I is issued in liquid^-/I₃ ^-Current potential).

Respectively by brown or yellow coloring from iodide (Figure 16 A (i)) or bromide (Figure 16 B (i)), reacting Formation element I (or Br being used, if using MABr) on Pb film in the process.

By comparing reaction film 1 hour (Fig. 6 B, 6C, 8A and 8B) of Pb immersed in MAI solution in the inclined of+0.75V Pressure reaction same time, reaction rate are obviously accelerated.In the film formed in the case where no application voltage, still detect { 111 } Pb at 31.2 ° of 2 angles θ⁰Peak, and the film for being formed under bias, Pb⁰Peak disappears (for MAPbI₃See Figure 16 A (iii) and to Br analog see Figure 16 B (iii)).

Conversion reaction can be slowed down by applying more negative potentials, and in -1.0V, the perovskite film of reaction transforms back into metal Pb (Figure 18).

Although certain features of the invention have been illustrated and described, those of ordinary skill in the art now will Expect many modification replacements, change and equivalent.It should therefore be understood that claim be intended to cover fall into it is of the invention real All such modifications and variations in spirit.

Claims

1. one kind is used to prepare formula A_uB_vX_wHalide perovskite or perovskite associated materials method；

Wherein:

X is at least one halide anions, pseudohalide anion or combinations thereof；

U is between 1-10；

V is between 1-10；

W is between 3-30；

B is at least one metal cation, wherein forming perovskite or the relevant material of perovskite when in conjunction with A and X；

Wherein the inorganic cation A is different from the metal cation B；

The method comprise the steps that

B metal or metal alloy layer is deposited on substrate；With

The B metal or metal alloy layer described in the solution comprising A and X or steam treated, wherein the solution or steam and the B Metal or metal alloy reaction, to form formula A in the surface of solids_uB_vX_wHalide perovskite or perovskite associated materials；

Or

The salt deposit containing A and X is deposited on substrate；With

Salt deposit described in steam treated with B metal or metal alloy；Wherein the B metal or metal alloy and the reactant salt, To form formula A on the surface of solids_uB_vX_wHalide perovskite or perovskite associated materials.

2. according to the method described in claim 1, the method comprise the steps that

B metal or metal alloy layer is deposited on substrate；And

The B metal or metal alloy layer described in the solution containing A and X or steam treated；The wherein solution or steam and the B Metal or metal alloy reaction, to form formula A on the surface of solids_uB_vX_wHalide perovskite or perovskite correlation material Material.

3. according to the method described in claim 1, the method comprise the steps that

Deposition includes the salt deposit of A and X on substrate；And

4. according to the method described in claim 1, wherein the perovskite material is by following formula ABX₃It indicates, in which:

A is at least one monovalence organic cation, inorganic cation or combinations thereof；

B is at least one metal cation, wherein forming perovskite material when in conjunction with A and X；And

X is at least one halide anions, pseudohalide anion or combinations thereof.

5. according to the method described in claim 1, wherein the halide perovskite associated materials are expressed from the next:

·A’₂A_n-1B_nX_3n+1Or A ' A_n-1B_nX_3n+1；N is between 1-9；

·A’₂A_mB_mX_3m+2Or A ' A_mB_mX_3m+2；M is between 1-9；Or

·A’₂A_q-1B_qX_3q+3Or A ' A_q-1B_qX_3q+3；Q is between 1-9；

Wherein

A ' is at least one monovalence or divalent organic cation, inorganic cation or combinations thereof；Wherein A and A ' is different；

B is at least one metal cation, wherein when with A and A ' and X in conjunction with when, formed halide perovskite associated materials；And And

X is at least one halide anions, pseudohalide anion or combinations thereof.

6. method according to any one of claims 1-5, wherein A be the organic sun of the monovalence comprising amido or ammonium from Son, wherein the amido or ammonium are primary, secondary or tertiary amido or ammonium.

7. method according to claim 1 to 6, wherein the B of the perovskite or perovskite associated materials Including metal cation, the oxidation state with (2+).

8. according to the method described in claim 7, wherein the B of the perovskite or perovskite associated materials includes (II) The metal cation of race's metal or (IV) race metal.

9. method according to claim 1 to 6, wherein the B of the perovskite or perovskite associated materials The mixture of metal cation and the metal of the oxidation state with (+3) or (+1) including the oxidation state with (+2).

10. method according to claim 1 to 9, wherein X is F^-、Cl^-、Br^-、I^-、SCN^-、NCS^-、NCSe^-、 NCTe^-、CN^-、NC^-、OCN^-、NCO^-、BH₄ ^-、OSCN^-、N₃ ^-、Co(CO)₄ ^-、C(NO₂)₃ ^-、C(CN)₃ ^-Or combinations thereof.

11. wherein A and X includes ammonium and halogen according to the method described in claim 1, wherein the solution or steam include A and X Compound, ammonium and pseudohalide, alkylammonium and halide, acid amidine and halide, acid amidine and pseudohalide, carbonamidine and halogenation Object, alkylammonium and pseudohalide, carbonamidine and pseudohalide wrap amine-containing organic cation and halide, the amine-containing organic sun of packet Ion and pseudohalide, monovalent metal cation and halide, monovalent metal cation and pseudohalide；Divalent metal With halide, divalent metal and pseudohalide, or combinations thereof.

12. method according to claim 1 or 2, wherein the method optionally further includes into the solution or steam External additive is added, wherein the external additive includes halogen (F₂、Cl₂、Br₂、I₂), HI, HCl, HBr, HF, HCN, S (CN)₂, alkyl halide, halogenated aryl hydrocarbon, haloheteroaromatic, halogenated cycloalkane, reducing agent, haloid, or combinations thereof.

13. method according to claim 1 or 3, wherein the method optionally further includes that outside is added into the salt Additive, wherein the external additive includes halogen (F₂、Cl₂、Br₂、I₂), HI, HCl, HBr, HF, HCN, S (CN)₂, halogenated Alkane, halogenated aryl hydrocarbon, haloheteroaromatic, halogenated cycloalkane, reducing agent, haloid, or combinations thereof.

14. method according to claim 1 to 13, wherein the perovskite or perovskite associated materials are MAPbI₃、MAPbBr₃、MAPb(I,Br)₃、FAPbI₃、FAPbBr₃、FAPb(I,Br)₃、CsPbI₃、CsPbBr₃、CsPb(I,Br)₃ Or (Cs, FA) Pb (I, Br)₃。

15. according to the method described in claim 1, wherein optionally heating the solution comprising A and X compound.

16. method described in any one of -15 according to claim 1, wherein to the deposition in the alcoholic solution comprising A and X B metal or metal alloy layer apply electrical bias.

17. the halide perovskite or perovskite associated materials of any one of -16 method preparation according to claim 1.

18. a kind of photoelectric device, including formula A_uB_vX_wHalide perovskite or perovskite associated materials；

Wherein:

X is at least one halide anions, pseudohalide anion or combinations thereof；

U is between 1-10；

V is between 1-10；

W is between 3-30；

Wherein the inorganic cation A is different from the metal cation B；

The wherein formula A_uB_vX_wPerovskite or perovskite associated materials be according to claim 1 any one of -16 method system Standby.

19. photoelectric device according to claim 18, wherein the halide perovskite associated materials are expressed from the next:

·A’₂A_n-1B_nX_3n+1Or A ' A_n-1B_nX_3n+1；N is between 1-9；

·A’₂A_mB_mX_3m+2Or A ' A_mB_mX_3m+2；M is between 1-9；Or

·A’₂A_q-1B_qX_3q+3Or A ' A_q-1B_qX_3q+3；Q is between 1-9；

Wherein

X is at least one halide anions, pseudohalide anion or combinations thereof.

20. a kind of photovoltaic cell, including formula A_uB_vX_wHalide perovskite or perovskite associated materials；

Wherein:

X is at least one halide anions, pseudohalide anion or combinations thereof；

U is between 1-10；

V is between 1-10；

W is between 3-30；

Wherein the inorganic cation A is different from the metal cation B；The wherein formula A_uB_vX_wPerovskite or perovskite Associated materials are prepared by according to claim 1 any one of -16 method.

21. photovoltaic cell according to claim 20 is expressed from the next wherein the Perovskite Phase closes material:

·A’₂A_n-1B_nX_3n+1Or A ' A_n-1B_nX_3n+1；N is between 1-9；

·A’₂A_mB_mX_3m+2Or A ' A_mB_mX_3m+2；M is between 1-9；Or

·A’₂A_q-1B_qX_3q+3Or A ' A_q-1B_qX_3q+3；Q is between 1-9；

Wherein

X is at least one halide anions, pseudohalide anion or combinations thereof.